Sulfonium halides and derivatives thereof



United States Patent 3,547,994 SULFONIUM HALIDES AND DERIVATIVES THEREOFKenneth Wayne Ratts, Creve Coeur, Mo., assignor to Monsanto Company, St.Louis, Mo., a corporation of Delaware No Drawing. Original applicationJune 28, 1965, Ser. No. 467,750, now Patent. No. 3,478,154, dated Nov.11, 1969. Divided and this application Nov. 13, 1967, Ser. No. 682,544

Int. Cl. C07c 103/00, 149/16, 149/34 US. Cl. 260561 9 Claims ABSTRACT OFTHE DISCLOSURE Sulfonium halides of the general formula wherein X ischloro, bromo or iodo, wherein R" and R are like or unlike lower alkyl,wherein A is lower alkoxy or a primary or secondary aliphatic amineresidue. These compounds are useful intermediates in preparinginsecticidal and fungicidal B-arylamino cinnamoyl compounds. The(N-substituted carbamoylmethyl) sulfonium halides are also fungicides.

This application is a division of copending application Ser. No.467,750, filed June 28, 1965, now US. Pat. 3,478,154.

This invention relates to new and useful sulfonium halides and to newand useful fi-arylamino cinnamoyl derivatives thereof.

The sulfonium halides of this invention can be represented by thegeneral formula wherein R is lower alkyl or lower alkenyl or loweralkoxyalkyl (e.g. methyl, ethyl, propyl, butyl, allyl, butenyl,methoxyethyl, ethoxyethyl, methoxypropyl, and the various isomeric formsthereof containing up to and including four carbon atoms) and wherein Ris hydrogen or lower alkyl or lower alkenyl or lower alkoxyalkyl (e.g.methyl, ethyl, propyl, butyl, allyl, butenyl, methoxyethyl, ethoxyethyl,methoxypropyl, and the various isomeric forms thereof containing up toand including four carbon atoms). It is preferred that X be chlorine,that R" and R be C alkyl (i.e. methyl or ethyl) and that both R and R beeither like lower n-alkyl or like lower n-alkenyl. This preferred groupis particularly useful as foliage fungicides, as for example controllingVenturia inaequalis (apple scab).

The sulfonium chlorides and bromides of this invention are prepared byreacting a sulfide of the formula RS wherein R" and R have theaforedescribed ice significance, with a substantially equimolecularproportion of an u-haloaceto compound of the formula 0 Z-CH l-A whereinZ is chlorine or bromine and wherein A has the aforedescribedsignificance, in a fiuid system (i.e. a reaction temperature above thefreezing point of the system up to and including the reflux temperatureof the system or the decomposition temperature of the sulfonium halide).Where and when desired an inert organic solvent can be used, e.g.benzene, toluene, xylene, hexane, heptane, octane, and the like. Thesulfonium iodides are prepared by mixing potassium iodide with aconcentrated aqueous solution of the appropriate sulfonium chloride insubstantially equimolecular proportions at room temperature, thesulfonium iodide product being less watersoluble than the sulfoniumchloride reactant precipitates out and is recovered by simplefiltration. Exemplary of the sulfide reactants are dimethyl sulfide,diethyl sulfide, di-n-propyl sulfide, diisopropyl sulfide, di-nbutylsulfide, methylethyl sulfide, ethylisopropyl sulfide, butylmethylsulfide, and the like. Exemplary of the a-haloaceto compound reactantsare N,N-dimethyl-a-chloroacetamide, N,N-diethyl-lac-chloroacetamide,N,N-diisopropyl-u-chloroacetamide, N methyl a chloroacetamide, N-ethyl-achloroacetamide, N-allyl-tat-chloroacetamide,N,N-diallyl-a-chloroacetamide, N-allyl-N-methyl-a-chloroacetamide, Nmethyl-N-isopropyl-a-chloroacetamide, N,Ndi(2-methoxyethyl)-a-chloroacetamide, N,N-di(2- ethoxyethyl) achloroacetamide, N-(Z-EthOXYethYD-occhloroacetamide,N-n-butyl-a-chloroacetamide, N,N-di-nbutyl-a-chloroacetamide, and thelike, and the corresponding u-bromoacetamides, and methyla-chloroacetate, ethyl a-chloroacetate, isopropyl a-chloroacetate,n-butyl u-chloroacetate, isobutyl a-chloroacetate, and the like, and thecorresponding a-bromoacetates.

The sulfonium halides of this invention are useful in preparingfi-arylamino cinnamoyl compounds of the general formula A1' C=OH- -Awherein A has the aforedescribed significance and prefer ence, andwherein Ar and Ar are like or unlike aryl having from 6 to 10 carbonatoms such as phenyl, alkylphenyl (e.g. tolyl, Xylyl, ethylphenyl,cumyl, cymenyl, butylphenyl, and the various isomeric forms thereof),and alkoxyphenyl (e.g. anisyl, dimethoxyphenyl, phenetyl,diethoxyphenyl, propoxyphenyl, butoxyphenyl, and the various isomericforms thereof). The B-arylamino cinnamides are fungicides while theparylamino cinnamoyl compounds are insecticidally active againstmosquito larvae.

The ,B-arylamino cinnamoyl compounds of this invention are prepared byinitially reacting substantially equimolecular proportions of sodiumhydride and a sulfonium halide of the aforedescribed formula underanhydrous conditions in the presence of tetrahydrofuran under a nitrogenatmosphere until an approximately equimolecular amount of hydrogenevolves, and thereafter adding to the reaction mass so obtained under anitrogen atmosphere a substantially equimolecular amount of a Schiifsbase of the formula ArCH NAr' wherein Ar and Ar have the aforedescribedsignificance. In the reaction between the sulfonium halide and sodiumhydride temperatures in the range of from about 10 C. to about 30 C.will be employed. In the reaction involving the Schiifs base anytemperature can be employed which provides a fluid system (i.e. areaction temperature above the freezing point of the system up to andincluding the reflux temperature of the system). Exemplary of theSchiffs O H C base reactants are benzalaniline,N-(p-methoxybenzylidene)aniline, N-(m-rnethoxybenzylidine)aniline,N-(m,p dimethoxybenzylidene) aniline, N- (p-ethoxybenzylidene) aniline,N-(m,p-diethoxybenzylidene)aniline, N-(p-methylbenzylidene)aniline, N(m,m' dimethylbenzylidene) aniline, N- (p-tert.butylbenzylidene)aniline,benzal-otoluidine, benZal-p-anisidine, benzal-p-phenetidine, benzalm,pdimethoxyaniline, benzal p methoxy-o-toluidine, N(m,p-dimethoxybenzylidene)-o-toluidine,N-(p-methoxybenzylidene)-p-phenetidine, (N-m-methylbenzylidene)-m,m'-xylidine, and the like.

As illustrative of this invention but not limitative thereof is thefollowing:

EXAMPLE I To a suitable reaction vessel equipped with a thermometer andagitator 75.1 parts by weight (substantially 1.2 moles) of dimethylsulfide and 149.6 parts by weight (substantially 1.0 mole) ofN,N-diethyl-o-chloroacetamide. The so charged mass is heated at about 40C. for fourteen hours, filtered and the filter cake dried underanhydrous nitrogen to give 98.9 parts by weight ofdimethyl(N,N-diethylcarbamoylmethyl)-sulfonium chloride enm-soH2iiN(cH5)21 01 which melts at 146l47.5 C.

EXAMPLE II To a suitable reaction vessel equipped with a vent,thermometer and agitator is charged 12.0 parts by weight (substantially0.05 mole) of dimethyl(N,N-diethylcarbamoylmethyl)-sulfonium chlorideand 350 parts by weight of anhydrous tetrahydrofuran. While agitatingthe so charged mass under a nitrogen atmosphere there is added 2.3 partsby weight (substantially 0.05 mole) of sodium hydride in the form of a 3by weight dispersion in mineral oil. The system is immediately connectedto a gas meter to observe the evolution of hydrogen. After agitating forabout two hours at room temperature approximately 0.1 part by Weight(substantially 0.05 mole) of hydrogen evolved. To the resulting reactionmass and while agitating under a nitrogen atmosphere is added 10.5 partsby weight (substantially 0.05 mole) of N-(p-methoxybenzylidene)-aniline.After agitating for one hour at room temperature the mass is then heatedat about 60 C. for one hour, whereupon the mass is cooled to roomtemperature and filtered. The filtrate is evaporated in vacuo and theyellow oily residue crystallized from pctroleum ether to give 10.5 partsby weight of fl-anilino- N,N-diethyl-p-methoxycinnamide which melts at108110 C.

EXAMPLE III Employing the procedure of Example I but replacingN,N-diethyl-wchloroacetamide with an equimolecular amount ofN,N-diethyl-a-bromoacetamide there is obtaineddimethyl(N,N-diethylcarbamoylmethyl)sulfonium bromide.

EXAMPLE IV Employing the procedure of Example II but replacingN-(p-methoxybenzylidene)aniline with an equimolecular amount ofN-(m,m-dimethylbenzylidene)aniline there is obtainedfi-anilino-N,N-diethyl-m,m'-dimethylcinnamide.

EXAMPLE V Employing the procedure of Example 11 but replacingN-(p-methoxybenzylidene)aniline with an equimolecular amount ofbenzalaniline [sometimes termed N-(benzylidenelaniline] there isobtained fi-anilino-N,N-diethylcinnamide which melts at 91-92 C.

4 EXAMPLE vr Employing the procedure of Example I but replacingN,N-diethyl-a-chloroacetamide with an equimolecular amount ofN,N-diallyl-a-chloroacetamide there is obtained dimethyl(N,Ndiallylcarbamoylmethyl)sulfonium chloride which melts at 12012l C.

EXAMPLE VII Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride andN-(p-methoxybenzylidene)aniline, respectively, with equimolecularproportions of dimethyl(N,N-diallylcarbamoylmethyl)sulfonium chlorideand benzalaniline there is obtained ,8-anilino-N,N-diallylcinnamidewhich melts at 9091 C.

EXAMPLE VIII Employing the procedure of Example I but replacingN,N-diethyl-a-chloroacetamide with an equimolecular amount ofN-n-propyl-a-chloroacetamide there is obtained dimethyl(Nn-propylcarbamoylmethyl)sulfonium chloride, a solid of hygroscopicnature.

EXAMPLE IX Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride with anequimolecular amount of dimethyl(N,n-propylcarbamoylmethyl)-sulfoniumchloride there is obtained ,8-anilino-N-n-propyl-p-methoxycinnamide.

EXAMPLE X Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride andN-(p-methoxybenzylidene)aniline, respectively, 'with equimolecularproportions of dimethyl(N-n-propylcarbamoylmethyl)sulfonium chloride andbenzalaniline there is obtained ,8-anilino-N-n-propylcinnamide whichmelts at l12113 C.

EXAMPLE XI Employing the procedure of Example I but replacingN,N-diethyl-a-chloroacetamide with an equimolecular amount of ethyla-bromoacetate there is obtained dimethyl(ethoxycarbonylmethyl)sulfoniumbromide.

which melts at 87 C.

EXAMPLE XII which melts at 67-68" C.

EXAMPLE XIII Employing the procedure of Example I but replacingN,N-diethyl-oc-chloroacetamide with an equimolecular amount of isopropyloz-chloroacetate there is obtaineddimethyl(isopropoxycarbonylmethyl)sulfonium chloride.

EXAMPLE XIV Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride with anequimolecular amount of dimethyl(isopropoxycarbonylmethyl)sulfoniumchloride there is obtained isopropyl ,B-anilino-p-methoxycinnamate.

EXAMPLE XV To a concentrated aqueous solution of dimethyl(N,N-diallylcarbamoylmethyl)sulfonium chloride is added in small incrementsan equimolecular amount of potassium iodide while agitating at roomtemperature. The mass is filtered and the filter cake dried underanhydrous nitrogen to give dimethyl(N,N-diallylcarbamoylmethyl)sulfoniumiodide which melts at 103l05 C.

EXAMPLE XVI Employing the procedure of Example XV but replacing dimethyl(N,N diallylcarbamoylmethyl)sulfonium chloride with an equimolecularamount of dimethyl(N,N- diethylcarbarnoylmethyl)sulfonium chloride thereis obtained dimethyl(N,N-diethylcarbamoylmethyl)sulfonium iodide.

EXAMPLE XVII Employing the procedure of Example XV but replacingdimethyl(N,N diallylcarbamoylmethyl) sulfonium chloride with anequimolecular amount of dimethyl(ethoxycarbonylmethyl)sulfonium bromidethere is obtained dimethyl(ethoxycarbonylmethyl) sulfonium iodide.

EXAMPLE XVIII Employing the procedure of Example I but replacingN,N-diethyl-ot-chloroacetamide with an equimolecular amount ofN-allyl-a-chloroacetamide there is obtained dimethylN,allylcarbarnoylmethyl) sulfonium chloride.

EXAMPLE XIX Employing the procedure of Example I but replacing dimethylsulfide with an equimolecular amount of diethyl sulfide there isobtained diethyl(N,N-diethylcarbamoylmethyl) sulfonium chloride.

EFQAMPLE XX Employing the procedure of Example I but replacing dimethylsulfide with an equimolecular amount of n-butylmethyl sulfide (i.e. n"CH -SCH there is obtained 11 butylmethyl(N,N diethylcarbamoylmethyl)sulfonium EXAMPLE XXI Employing the procedure of Example I but replacingN,N-diethyl-tx-chloroacetamide with an equimolecular amount ofN-methyl-N-isopropyl-a-chloroacetamide there is obtained dimethyl(N-methyl-N-isopropylcarbamoylmethyl sulfonium chloride.

EXAMPLE XXII Employing the procedure of Example I but replacingN,N-diethyl-a-chloroacetamide with an equimolecular amount ofN,N-di(2-ethoxyethyl) chloroacetamide there is obtaineddimethyl[N,N-di(2-ethoxyethyl)carbamoylmethyl] sulfonium chloride.

EXAMPLE XXIII Employing the procedure of Example II but replacingN-(p-methoxybenzylidene)aniline with an equimolecular amount ofbenzal-p-anisidine there is obtained ,B-p-anisidino-N,N-diet'hylcinnamide Employing the procedure of Example II but replacingN-(p-methoxybenzylidene)aniline with an equimolecular amount ofbenzal-p-methoxy-o-toluidine there is obtained 5-(p-methoxy-o-toluidino) -N,N-diethylcinnamide.

EXAMPLE XXV Employing the procedure of Example II but replacingN-(p-methoxybenzylidene)aniline with an equimolecular amount ofN-(p-ethoxybenzylidene)-p-toluidine there is obtainedp-(p-toluidino)-N,N-diethyl-p-ethoxycinnamide.

6 EXAMPLE xxvr Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride with anequimolecular amount of dimethyl(N-allylcarbamoylmethyl)sulfoniumchloride there is obtained p-anilino-N-allyl-p-methoxycinnamide.

EXAMPLE XXVII Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride andN-(p-rnethoxybenzylidene)aniline, respectively, with equimolecularproportions of dimethyl(N-methyl-N- isopropylcarbamoylmethyl)sulfoniumchloride and benzalaniline there is obtained[3-anilino-N-methyl-N-isopropylcinnamide.

EXAMPLE XXVIII Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride andN-(pmethoxybenzylidene)aniline, respectively, with equimolecularproportions of dimethyl[N,N-di(2- ethoxyethyl)carbamoylmethyl]sulfoniumchloride and N- (m,p-dimethoxybenzylidene)aniline there is obtained ,8-anilino-N,N-di (Z-ethoxyethyl) -m,p-dimethoxycinnamide.

EXAMPLE XXIX Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride and N-(pmethoxybenzylidene)aniline, respectively, with equimolecular proportionsof dimethyl(N,Ndiallylcarbamoylmethyl)sulfonium iodide andbenzal-p-tert. butylaniline there is obtained B-(p-tert.butylanilino)-N,N- diallylcinnamide.

EXAMPLE XXX Employing the procedure of Example II but replacingdimethyl(N,N diethylcarbarnoylmethyl)sulfonium chloride andN-(p-methoxybenzylidene)aniline, respectively, with equimolecularproportions of dimethyl(ethoxycarb0nylmethyl)sulfonium iodide andbenzal-o-toluidine there is obtained ethyl ,B-(o-toluidino)cinnamate.

Other sulfonium halides and B-arylamino cinnamoyl compounds which can beprepared in accordance with the procedures of this invention includedimethyl(N-methylcarbamoylmethyl)sulfonium chloride, dimethyl(N-ethylcarbamoylmethyl sulfonium chloride, dimethyl(N-isopropylcarbamoylmethyl sulfonium chloride, dimethyl(N-isobutylcarbamoylmethyl sulfonium chloride, dimethyl(N-n-but-2-enylcarbamoylmethyl) sulfonium chloride, dimethyl [N-(Z-methoxyethyl) carbamoylmethyl] sulfonium chloride,

diethyl(N-n-propylcarbamoylmethyl)sulfonium chloride,

diethyl (N,N-dimethylcarb amoylmethyl) sulfonium chloride,

diethyl N,N liallylcarbamoylmethyl sulfonium chloride,

diethyl (N,N-dibut-Z-enylcarbamoylmethyl) sulfonium chloride,

diethyl N,N-di-n-butylcarb am oylrnethyl sulfonium chloride,

diethyl (N-methyl-N-iso pro pylcarbamoylmethyl) sulfonium chloride,

methylethyl (N,N-diallylcarb am oylrnethyl sulfonium chloride,

methylethyl (N,N-dimethylcarbamoylrnethyl) sulfonium chloride,

diisopropyl(N,N-diallylcarbamoylmethyl)sulfonium chloride,

di-n-butyl (N,N-dial1ylcarbamoylmethyl sulfonium chloride,

dimethyl(methoxycarbonylrnethyl)sulfonium chloride,

diethyl(ethoxycarbonylmethyl)sulfonium chloride,

methylethyl (ethoxycarbonylmethyl) sulfonium chloride,

methylethyl (isopropoxycarbonylmethyl) sulfonium chloride,

diisopropyl methoxycarbonylmethyl sulfonium chloride,

di-n-butyl(isobutoxycarbonylmethyl)sulfonium chloride,

and

the correspondig sulfonium bromides and sulfonium iodides;

B-anilino-N-methylcinnamide,

p-anilino-N-ethylcinnamide,

B-anilino-N-isopropylcinnamide,

[B-anilino-N-n-butylcinnamide,

,8-anilino-N,N-dimethylcinnarnide,

B-anilino-N,N-dimethyl-p-ethoxycinnamide,

B-anilino-N,N-di-n-butylcinnamide,

fl-anilino-N-allylcinnamide,

B-anilino-N-allyl-o-methylcinnamide,

fl-anilino-N- Z-methoxyethyl) cinnamide,

B-anilino-N,N-di-n-propylcinnamide,

,B-anilino-N,N-dibut-Z-enylcinnamide,

B-(o-toluidino)-N,N-diallylcinnamide,

)3- p-anisidino) -N,N-diallylcinnamide,

,8- (p-anisidino -N,N-diallyl-p-isobutoxycinnamide,

pm-phenetidino -N-allylcinnamide,

B- m-phenetidino -N-allyl-p-isopropylcinnamide,

pm-phenetidino -N-isopropylcinnamide,

fip-isopropylanilino -N,N-dimethylcinnamide,

,8- m,p-diethoxyanilino -N,N-dimethylcinnamide,

fi-(p-isobutoxyanilino)-N,N-di-n-propylcinnamide,

,8- o-anisidino) -N- Z-methoxyethyl cinn amide,

3- (p-anisidino -N-methyl-N-isopropylcinnamide,

B-(p-toluidino)-N-methyl-N-isopropylcinnamide,

methyl ,B-anilinocinnamate,

ethyl 18-anilino-p-isopropylcinnamate,

isopropyl fi-anilinocinnamate,

isopropyl {3-anilino-m-ethoxycinnamate,

n-butyl B-anilinocinnamate,

methyl 5- m-anisidino cinnamate,

ethyl fl-(p-phenetidino)cinnamate,

methyl ,8-(m,p-dimethoxyanilino)cinnamate,

ethyl fl- (p-isobutoxyanilino cinnamate,

and the like.

The effectiveness of the compounds of this invention as fungicides isillustrated below.

Slide germination test: By the slide germination test the concentrationof the compound to be evaluated required to inhibit complete germinationof spores from 7- to 10-day old cultures of Venturia inaequalis isdetermined. 1.0 gram of the compound (below itemized) is dissolved inacetone to make a concentrated solution thereof and thereto is added andintimately mixed 0.1 gram of sorbitan monolaureate polyoxyethylenederivative (a commercial water-soluble non-ionic emulsifying agent).Thereto is added and intimately mixed sufficient water to provide anaqueous emulsion containing 10 p.p.m. of the compound. To a test tube isthen added four volumes of the aqueous emulsion and one volume of sporestimulant and one volume of spore suspension, the spore stimulant beingadded to insure a high and relatively stable percentage of germinationin the control. Drops of the test specimen mixture and an untreatedcontrol are pipetted onto glass slides. The glass slides are then placedin moist chambers for hours incubation at 22 C. Germination counts aremade by counting 100 potentially viable spores, i.e. those spores whichwould germinate under the normal conditions of the control. The resultswere as follows:

Compound:

Dimethyl(N,N diallylcarbamoylmeth- Germination yl sulfonium bromide NoneDimethyl(N,N diallylcarbamoylmethyl sulfonium iodide Do. Dimethyl(N,Ndiallylcarbamoylmethyl) sulfanium chloride Do. Dimethyl(N Npropylcarbamoylmethyl) sulfonium chloride Do.

8 Compound: Germination p-Anilino-N,N-diethylcinnamide None,B-Anilino-N,N-diallylcinnamide Do. Control Complete.

In a similar evaluation against the late blight fungus Phytopht/zorainfestans at respective concentrations of 10 p.p.m. dimethyl(N,N-diallylcarbamoylmethyl) sulfonium bromide,dimethyl(N-n-propylcarbamoylmethyl)sulfonium chloride andfl-anilino-N,N-diethylcinnamate, respectively, completely preventedgermination of spores of said fungus.

With respect to the soil fungus Pythium ultimum at a concentration of 30p.p.m. dimethyl(N,N-diallylcarbamolylmethyl)-sulfonium bromide andfi-anilino-N,N-diethyl-p-methoxycinnamide, respectively, exhibitedcomplete control of the said soil fungus.

As aforementioned the alkyl ,B-arylamino cinnamates of this inventioneffectively control mosquito larvae. For example at a concentration of10 p.p.m. ethyl B-anilinocinnamate exhibited a kill of yellow fevermosquito larvae, Aedes aegypti,

The exact concentration of the fungicidal or insecticidal agents of thisinvention employed in combatting or controlling fungi or insects canvary considerably provided the required dosage (i.e., a toxic amount)thereof is supplied to the respective organisms or to the environment ofthe organisms. When the extending agent is a liquid or mixture ofliquids (e.g. as in solutions, suspensions, emulsions, or aerosols) theconcentration of the fungicidal or insecticidal agent employed to supplythe desired dosage generally will be in the range of 0.001 to 50 percentby weight. When the extending agent is a semi-solid or solid, theconcentration of the fungicidal or insecticidal agent employed to supplythe desired dosage generally will be in the range of 0.1 to 25 percentby weight. From a practical point of view, the manufacturer must supplythe agriculturist with a low-cost concentrate or spray base orparticulate solid base in such form that, by merely mixing with water orsolid extender (e.g., powdered clay or talc) or other low-cost materialavailable to the agriculturist at the point of use, he will have aneasily prepared fungicidal or insecticidal spray or particulate solid.In such a concentrate composition, the fungicidal or insecticidal agentgenerally will be present in a concentration of 5 to percent by weight,the residue being any one or more of the well-known fungicidal orinsecticidal adjuvants, such as the various surface active agents (e.g.,detergents, a soap or other emulsifying or wetting agent, surface-activeclays), solvents, diluents, carrier media, adhesives, spreading agents,hurnectants, and the like.

In controlling or combatting fungal organisms or insects the fungicidalor insecticidal agents of this invention either per se or compositionscomprising same are supplied to the fungi or insects or to theirenvironment in a toxic amount. This can be done by dispersing the newfungicidal or insecticidal agent or fungicidal or insecticidalcomposition Comprising same in, on or over an infested environment orin, on or over an environment the fungi or insects frequent, e.g.agricultural soil or other growth media or other media infested with thefungi or insects, or attractable to the fungi or insects forhabitational or sustenance or propagational purposes, an anyconventional fashion which permits contact between the organisms and thefungicidal or insecticidal agents of this invention. Such dispersing canbe brought about by applying the fungicidal agent per se or sprays orparticulate solid compositions containing same to a surface infestedwith the fungi or insects or attractable to same, as for example, thesurface of agricultural soil or other media such as the above groundsurface of plants by any of the conventional methods, e.g. powerclusters, boom and hand Sprayers, and spray dusters. Also forsub-surface application such dispersing can be carried out by simplymixing the new fungicidal or insecticidal agent per se or fungicidal orinsecticidal spray or particulate solid compositions comprising samewith the infested environment or with the environment the fungi orinsects frequent, or by employing a liquid carrier for the newfungicidal or insecticidal agent to accomplish sub-surface penetrationand impregnation therein.

What is claimed is:

1 A sulfonium halide of the formula wherein X is halogen of atomicweight in the range of 35 to 127, wherein R" and R' are lower alkyl, andwherein A is wherein R is selected from the group consisting of loweralkyl, lower alkenyl and lower alkoxyalkyl and wherein R is selectedfrom the group consisting of hydrogen, lower alkyl, lower alkenyl andlower alkoxyal'kyl.

2. A compound of claim 1 wherein X is chloro, wherein R" and R' are Calkyl and wherein R and R are like lower n-alkyl.

3. A compound of claim 1 wherein X is chloro, where in R" and R' are Calkyl and wherein R and R are like lower n-alkenyl.

4. A compound of claim 2 which is dimethyl(N,N-diethylcarbamoylmethyl)sulfonium chloride.

5. A compound of claim 3 which is dimethyl(N,N-diallylcarbamoylmethylsulfonium chloride.

6. A compound of claim 2 which isdimethyl(N,n-propylcarbamoylmethyl)sulfonium chloride.

7. A compound of claim 1 which is dimethyl(N,N-diallylcarbamoylmethyl)sulfonium iodide.

8. The method of making a sulfonium halide of the 10 wherein Z isselected from the group consisting of chlorine and bromine, wherein R"and R" are lower alkyl, and wherein A is wherein R is selected from thegroup consisting of lower alkyl, lower alkenyl and lower alkoxyalkyl andwherein R is selected from the group consisting of hydrogen, loweralkyl, lower alkenyl and lower alkoxyalkyl, which comprises reactingequimolecular proportions of a sulfide of the formula 'R"-SR with analpha-haloaceto compound of the formula 0 ZCH C A UNITED STATES PATENTS8/1968 Payne 260-464 12/1950 Stewart 260561X OTHER REFERENCES Scheele eta1. Chem. Abs. vol. 52: 15418-9 (1958).

ALEX MAZE, Primary Examiner J. A. NA-RCAVAGE, Assistant Examiner US. Cl.X.-R.

